Water → Ethyl difluoro(6-methylpyridazin-3-yl)acetate

HRID 1357943Notes

Reaction equation

HRID 1357943 reaction equation
[F:1][C:2]([F:9])(I)[C:3]([O:5][CH2:6][CH3:7])=[O:4].Br[C:11]1[N:12]=[N:13][C:14]([CH3:17])=[CH:15][CH:16]=1.O.[NH4+].[Cl-]>CS(C)=O.[Cu]>[F:1][C:2]([F:9])([C:11]1[N:12]=[N:13][C:14]([CH3:17])=[CH:15][CH:16]=1)[C:3]([O:5][CH2:6][CH3:7])=[O:4]

Participants

7

Reactant 4

HCID 962WaterHCID 25517Ammonium ChlorideHCID 2737200Ethyl difluoro(iodo)acetateHCID 119590863-Bromo-6-methylpyridazine

Product 1

HCID 69558022Ethyl difluoro(6-methylpyridazin-3-yl)acetateYield 97.1%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolvent2×

Procedure

This procedure is derived from the general method of T. Taguchi, et al. (Tetrahedron Lett., 1986, 27, 6103-6106). Ethyl difluoroiodoacetate (0.355 mL, 651 mg, 2.60 mmol) was added to a rapidly stirred suspension of copper powder (333 mg, 5.24 mmol) in DMSO (6.5 mL) at rt. After 50 min., 3-bromo-6-methylpyridazine (300 mg, 1.73 mmol) was added in DMSO (1.0 mL). After 20 h, the mixture was transferred to a separatory funnel containing water (25 mL) and saturated aq. NH4Cl (25 mL), and extracted with ethyl acetate (2×50 mL). The organic extracts were washed with saturated aq. brine, dried (sodium sulfate), decanted, and evaporated. Purification by flash column chromatography on silica gel, eluting with 70:30 v/v hexanes/ethyl acetate, gave 363 mg of the title compound as an amber liquid. For the title compound:

Workup

  1. waitAfter 20 h
  2. customthe mixture was transferred to a separatory funnel
  3. extractionextracted with ethyl acetate (2×50 mL)
  4. washThe organic extracts were washed with saturated aq. brine
  5. dry with materialdried (sodium sulfate)
  6. customdecanted
  7. customevaporated
  8. customPurification by flash column chromatography on silica gel
  9. washeluting with 70:30 v/v hexanes/ethyl acetate

Sources & evidence

ORD record
ord-726048f0ccc44fd395df3e4a13334032
Source dataset
uspto-grants-2003_07
Patent number
US06593346B2

Reaction notes

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